Abstract

LiCoO 2/mesocarbon microbeads (MCMB) batteries are over-charged to different voltage (4.4 V, 4.5 V, 4.6 V, and 4.7 V, respectively) for ten times, and then are cycled 1000 times for shallow depth of discharge. The morphology, structure, and electrochemical performance of the electrode materials were studied in detail in order to identify the capacity fading mechanism of over-charged battery after long-term cycling. The cycling performances of LiCoO 2/MCMB batteries are gradually aggravated with the increase of over-charging voltage and the degradation mechanism is diverse upon the degree of over-charging. Furthermore, the capacity fading after long-term cycling of battery over-charged to 4.6 V or 4.7 V is mainly attributed to the cathodes. Soft X-ray absorption spectroscopy (XAS) demonstrates that the lower valence state of cobalt exists on the surface of the LiCoO 2 after serious over-charging (4.6 V or 4.7 V), and cobalt is dissolved then deposited on the anode according to the result of energy dispersive spectrometry (EDS). But, after shallow over-charging (4.4 V or 4.5 V), the capacity deterioration is proposed as the loss of active lithium, presented by the generation of the SEI film on the anode, which is verified by water washed tests.

@article{osti_1360192,
title = {Degradation mechanism of over-charged LiCoO2/mesocarbon microbeads battery during shallow depth of discharge cycling},
author = {Zhang, Lingling and Ma, Yulin and Cheng, Xinqun and Cui, Yingzhi and Guan, Ting and Gao, Yunzhi and Du, Chunyu and Yin, Geping and Lin, Feng and Nordlund, Dennis},
abstractNote = {LiCoO2/mesocarbon microbeads (MCMB) batteries are over-charged to different voltage (4.4 V, 4.5 V, 4.6 V, and 4.7 V, respectively) for ten times, and then are cycled 1000 times for shallow depth of discharge. The morphology, structure, and electrochemical performance of the electrode materials were studied in detail in order to identify the capacity fading mechanism of over-charged battery after long-term cycling. The cycling performances of LiCoO2/MCMB batteries are gradually aggravated with the increase of over-charging voltage and the degradation mechanism is diverse upon the degree of over-charging. Furthermore, the capacity fading after long-term cycling of battery over-charged to 4.6 V or 4.7 V is mainly attributed to the cathodes. Soft X-ray absorption spectroscopy (XAS) demonstrates that the lower valence state of cobalt exists on the surface of the LiCoO2 after serious over-charging (4.6 V or 4.7 V), and cobalt is dissolved then deposited on the anode according to the result of energy dispersive spectrometry (EDS). But, after shallow over-charging (4.4 V or 4.5 V), the capacity deterioration is proposed as the loss of active lithium, presented by the generation of the SEI film on the anode, which is verified by water washed tests.},
doi = {10.1016/j.jpowsour.2016.08.030},
journal = {Journal of Power Sources},
number = C,
volume = 329,
place = {United States},
year = {Fri Aug 26 00:00:00 EDT 2016},
month = {Fri Aug 26 00:00:00 EDT 2016}
}

Among all primary lithium batteries, Li/CF x primary battery possesses the highest energy density of 2180 Wh kg -1. However, a key limitation is its poor rate capability because the cathode material CF x is intrinsically a poor electronic conductor. Here, we developed a so-called “doing subtraction” method to modify the pinecone shaped fluorinated mesocarbon microbead (F-MCMB). The modified fluorinated mesocarbon microbead (MF-MCMB), manifests the advantage of open-framed structure, possesses good electronic conductivity and removes transport barrier for lithium ions. Thus, high capacity performance and excellent rate capability without compromising capacity can be obtained. A capacity of 343 mAhg -1more » and a maximum power density of 54600 W kg -1 are realized at an ultrafast rate of 40 C (28A g -1). Additionally, the MF-MCMB cathode does not show any voltage delay even at 5C during the discharge, which is a remarkable improvement over the state-of-the-art CF xmaterials.« less

The charge-discharge reaction mechanism of the graphitized mesocarbon microbead (MCMB) anode was investigated with cyclic voltammetry and X-ray diffractometry. It is concluded that the charge-discharge reaction of graphitized MCMB involves intercalation of lithium, which is essentially similar to that for graphite. However, the in-plane ordering of the stage 1 and 2 Li-GICs (Graphite Intercalation Compounds) obtained from the graphitized MCMB is not LiC{sub 6} like graphite, but is close to LiC{sub 8}, according to the results of both X-ray diffractometry and cyclic voltammetry.

For designing new battery systems with higher energy density and longer cycle life, it is important to understand the degradation mechanism of the electrode material, especially at the individual particle level. Using in situ transmission X-ray microscopy (TXM) coupled to a pouch cell setup, the inhomogeneous Li distribution as well as the formation, population, and evolution of inactive domains in a single LiCoO 2 particle were visualized in this paper as it was cycled for many times. It is found that the percentage of the particle that fully recovered to the pristine state is strongly related to the cycling rate.more » Interestingly, we also observed the evolution of the inactive region within the particle during long-term cycling. The relationship between morphological degradation and chemical inhomogeneity, including the formation of unanticipated Co metal phase, is also observed. Finally, our work highlights the capability of in situ TXM for studying the degradation mechanism of materials in LIBs.« less